Pkocess foe producing l-acyloxy-j



Patented Sept. 26, 1950 PROCESS FOR PRODUCING 1-ACYLOXY-3- BUTENE-Z-ONESJoseph M. Wilkinson, .lr., Easton, Pa., assignor to General Aniline &Film Corporation, New York, N. Y., a corporation of Delaware N Drawing.Application November 14, 1947,

Serial No. 786,161

This invention relates to an improved method for the production ofI-acyloxy-3 butene-2-ones 2 Claims. "(01. 260-4 91) by the isomerizationof the corresponding l-acyl- I oxy-4-hydroxy-2-butyne.

Certain 1-acyloxy-3-butene-2-ones(particularly1-acetoxy-3-butene-2-ones) have heretofore been describedand are known to be easily polymerizable substances whose polymerresembles polyvinyl acetatein appearance.

I have now discovered that 1-acyloxy-3-butene- 2-one may readily beobtained from the isometric l-acyloxy-4-hydroxy-2-butyne by treating asolution thereof with a mercuric ion catalyst. The course of thereaction, as well as the type of reactants which maybe employed'and theproducts produced, may be summarized with reference to the followingequation:

Rtt-o-oH o o-on OH HEH RH- r twherein R stands for the. residue of afatty acid.

The process of the present invention will be apparent to those skilledin the art from a consideration of the following specific example, inwhich the parts are by weight:

Example 128 grams (1 mol) of 1-acetoxy-2-butyne-4- a 2 able catalystsmaybe mentioned mixtures of mercuric oxide and boron trifiuorideandacidic mixtures of mercuric sulfate, such as mercuric sulfate insulfuric acid. 1

It will also be understood that the acyloxy group present in theunsaturated ketone obtained as a product will correspond to the acyloxygroup present in the acetylenic half ester employed as the startingmaterial. As examples of l-acyloxy- 3-butene-2-ones which may readily beisomerized to the corresponding l-acyloxyl-hydroxy- Z-butynes may bementioned the half esters of acetylenic diols of the type described inmy oo- 01 were dissolved in 200 cc. of acetone containample illustratesa specific embodiment of the present invention and that various changesmay be made therein Without departing from the spirit of the presentinvention or the scope of the appended claims. Thus, in place of theacetone employed in the specific example, the process has beensuccessfully operated using such solvents as water, aqueous acetic acidand glacial acetic acid and it appears that anyinert solvent iseffective and may be used in amounts sufficient to give a readily-fluidreaction mass. Likewise, it is to be understood that in place ofmercuric sulfate employed in the above example, the isomerization of thepresent invention may be catalyzed by any mercuric ion catalysts. Asexamples of suitpending application Serial No. 786,162, filed No-.vember 14, 1947, now Patent No. 2,520,750, such as the half esters. oflower aliphatic acids such as acetic, propionic, butyric, isobutyric andvaleric acids and of higher fatty acids such as capric, lauric,myristic, palmitic and stearic acid. Of these the half esters of thesaturated lower aliphatic acids, particularly acetic acid, yieldproducts having the widest field of utility and are therefore preferred.

As indicated by the foregoing example, the reaction of the presentinvention is exothermic, particularly when the half esters of loweraliphatic acids with 2-butyne-1A-diol are employed and proceeds readilywithout outside heating; With the half esters of higher fatty acids,some slight heating may be necessary to initiate a reaction and, ifnecessary, the reaction mixture may be warmed up to a temperature of sayC, and maintained at this temperature in order to eiTect the desiredisomerization reaction at an economical rate.

I claim:

1. The method of producing 1-acyloxy-3- butene-2-ones, which comprisessubjecting 1- acyloxy l-hydroxy-2-butyne to the action of v a mercuricion catalyst in the presence of an inert solvent. 1

2. The process of producing l-acetoXy-3-butene-2-one, which comprisessubjecting l-acetoxy-4-hydroxy-2-butyne to the action of a mercuric ioncatalyst in the presence of an inertsolvent.

' JOSEPH M. WILKINSON, JR.

REFERENCES CITED Abstract of an article from Bull. Soc. Chim. 11 (1944),pgs. 514-515.

Lozach Chemical Abstracts, vol. 40, col. 2114

1. THE METHOD OF PRODUCING 1-ACYLOXY-3BUTENE-2-ONES, WHICH COMPRISESSUBJECTING 1ACYLOXY-4-HYDROXY-2-BUTYNE TO THE ACTION OF A MERCURIC IONCATALYST IN THE PRESENCE OF AN INERT SOLVENT.